Water soluble alkylolamides



United States Patent 3,281,438 WATER SOLUBLE ALKYLOLAMIDES Keith Liddell Johnson, Park Forest, Ill., assignor to Swift & Company, Chicago, Ill., a corporation of Illinois No Drawing. Filed May 23, 1962, Ser. No. 196,868 6 Claims. (Cl. 260-404) This invention relates to new compositions of matter and more specifically to improved fatty alkanolamides and to methods for manufacturing such fatty alkanolamides.

Fatty alkylolamides represent an important group of organic compositions having surface active properties and these materials have been employed in the past as emulsifying agents, detergents, wetting agents, and generally as surface tension reducing agents in aqueous media. The usageof these fatty alkylolamides on a large scale has been limited to a certain degree because of the fact that these compositions possess limited solubility in water and they are even less effective in aqueous solutions containing electrolytes. The development of alkylolamides having a high amide content has increased these difficulties inasmuch as the high amide alkylolamides are even less soluble in aqueous solutions than conventional commercial alkylolamides. An additional shortcoming exhibited by these fatty alkylolamides is the tendency for these materials and/or their corresponding amine esters to saponify in alkaline systems yielding soaps which, when they come in contact with hard water, act as defoaming agents.

The improved fatty alkylolamides of this invention can be formulated to exhibit a high degree of solubility in water and they are also characterized by the fact that the hard water salts of the soaps formed on saponification of these materials are sufliciently soluble so that no defoaming action is encountered.

It is therefore an object of this invention to provide new surface active higher fatty alkylolamides which are more soluble in water and aqueous electrolyte solutions than fatty alkylolamides knOVim heretofore.

An additional object of the invention is the provision of higher fatty alkylolamides having oxyalkylene substituents on the fatty chain of said alkylolamides.

Still another object of the invention is to provide improved methods for preparing highly active chain substituted fatty alkylolamides.

Additional objects, if not specifically set forth herein, will be readily apparent to those skilled in the art from the detailed description of the invention which follows.

Generally, the invention relates to compositions comprising condensation products of alkylolamides and chain substituted higher fatty acids of 10-30 carbons. The substitution on the fatty chain or hydrophobic portion of the molecule appears to impart to the fatty alkylolamide a strong water solubilizing effect and renders the composition highly active, apparently as a result of a unique hydrophilic-lipophilic balance. The chain substituted fatty alkylolamides of the invention are not so limited as are the previously known fatty alkylolamides in systems containing large amounts of water or aqueous solutions of electrolytes. Thus, the substituted fatty alkylolamides of this invention exhibit good water solubility and substantial activity in aqueous solutions containing electrolytes. For this reason the compositions can be used in a number of aqueous systems in which previously recognized fatty alkylolamides have been found to be of limited value. Furthermore, certain of the chain substituted higher fatty alkylolamides possess properties rendering them useful as metal working lubricants.

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More specifically, the compositions of this invention comprise alkylolamides of higher fatty acids with the aliphatic hydrocarbon chain of the fatty acid being substituted with oxyalkylene groups. The oxyalkylene substitution appears to profoundly affect the water solubility and surface tension reducing properties of the alkylolamide. Both monoand dialkylolamides are contemplated and the type and molecular size of the oxyalkylene substitution can be varied widely. The compositions may be characterized by the structural formula:

where W and X are selected from the group consisting of H, OH and oxyalkylene and at least one of W and X is oxyalkylene; R is selected from the group consisting of H, lower alkylol, lower alkyl, and lower alkylamino. R is lower alkylol and m is 0-19; n is 0-4; p is 0-19; y is O-17; and m+2n+ny+3+p =929.

The compositions are monoor dialkylolamides of higher fatty acids having oxyalkylene groups substituted about 1-4 times along the fatty chain. In some cases, as will appear hereinafter, hydroxyl groups may also be substituted on the fatty chain adjacent to the oxyalkylene substitution. The oxyalkylene substituent is attached to the fatty chain by an oxygen ether linkage and this group can be a simple alkylene oxide radical such as -(CH CH O). H or an ether or ester derivative thereof. Typical ether radicals are where R is lower alkyl, phenyl or phenyl radical having nuclear alkyl substituents and n is 1-20. A typical oxyalkylene ester structure is (CH CH O),,OOR where R is an alkyl or alkenyl radical of 10-30 carbons and n is 1-20. While the structure exemplifying the oxyalkylene substituent shows ethyleneoxy groups, it should be understood that other lower alkyleneoxy groups such as propyleneoxy and butyleneoxy groups are also contemplated. The oxyalkylene substituent can be represented by the formula (YO),,Z where Y is an alkylene group of 2-4 carbons, n is 1-100, preferably l-20, and Z is selected from the group consisting of carboxy acyl, phenyl, lower alkyl, H, and nuclear substituted phenyl radicals.

The oxyalkylated higher fatty acid alkylolamides can be prepared from hydroxy substituted higher fatty acid esters and oxirane substituted higher fatty acid esters. Esters of hydroxy substituted higher fatty acids are alkoxylated by contacting the hydroxylated material with a 1,2-alkylene oxide in the presence of an alkaline catalyst. The reaction is exothermic in nature and generally takes place at a temperature below about 70 C. and above about 20 C. A variety of alkaline catalysts can be used to initiate the reaction, although the alkali metal lower alkoxides such as sodium methoxide and sodium ethoxide and alkali metal hydroxides, such as sodium hydroxide, are preferred.

In accordance with this procedure, it is possible to substitute polyethyleneoxy, polypropyleneoxy or polybutyleneoxy groups on the fatty chain at the position in the starting ester occupied by the hydroxyl group. Thus, lower alkyl esters of hydroxy substituted higher fatty acids, such as methyl, ethyl or propyl IZ-hydroxystearate, methyl ricinoleate or ethyl dihydroxystearate may be oxyalkylated by this procedure. The lower glycol and glycerol esters of hydroxy substituted higher fatty acids can also be treated in this manner to provide oxyalkylated esters. Specific materials coming within this group of hydroxylated materials, which can be employed as starting materials, include such substances as ethylene glycol diricinoleate, castor oil, hardened castor oil, hydroxylated animal, vegetable and marine glycerides and mixtures thereof. The monohydric alcohol esters of hydroxy substituted fatty acids derived from naturally occurring triglycerides are also suitable. The number of oxyalkylene groups substituted on the fatty chain can vary from about 1 to 100, depending upon the characteristics desired in the final product. Alkylene oxides which can be employed to alkoxylate the hydroxylated fatty acid esters include 1,2-epoxy propane, 2,3-epoxy butane and ethylene oxide as Well as 'epichlorohydrin.

Another embodiment of the method of the invention, which can be employed to produce the chain substituted higher fatty acid ester which is then amidated with the amino alcohol, involves the alkoxylation of oxirane substituted higher fatty acid derivatives. 'In copending application, Serial No. 177,968, filed March 7, 1962, the production of oxyalkylated higher fatty acid esters is de scribed. These compositions are prepared by reacting oxirane substituted higher fatty acid derivatives with dihydric aliphatic alcohols, monohydric aliphatic alcohol ethers or monohydric aliphatic alcohol esters to produce mono-, diand trihydric alcohol esters of oxyalkylene substituted higher fatty acids. Because the polyoxyalkylene alcohols are reacted with oxirane substituted higher fatty acid esters, the oxyalkylated higher fatty ester also possesses hydroxyl groups substituted on the fatty chain on the carbon adjacent to the carbon containing the oxyalkylene group. These compositions are prepared by mixing and reacting the oxirane substituted higher fatty acid ester with a polyoxyalkylated alcohol in the presence of a catalytic amount of a Friedel-Crafts catalyst such as the boron halides, boron trifluoride and boron trichloride as well as lower ether and alcohol complexes with these boron halides. Other suitable catalysts which vary in effectiveness, depending upon the specific alcohol and epoxide being combined, include the halides of iron, al-uminu-m, tin, arsenic, antimony, zinc and zirconium. Antimony pentachloride and tin tetrachloride, in addition to the boron halides and complexes thereof, represent a preferred group of catalysts. The reaction is exothermic in nature and usually is initiated at room temperature (about 20 0.). Some of the alkoxylating alcohols are less reactive than others and it may be necessary to use moderate heating to about 70 C. to initiate the reaction.

Oxirane substituted compositions which can be employed in producing the oxyalkylene substituted higher fatty acid ester include the oxirane substituted higher fatty acid derivatives. The oxirane containing higher fatty acids (30 carbons), and derivatives thereof, represent a very convenient source of the oxirane reactant. Epoxidized animal, vegetable and marine triglycerides are well known in the art and examples of these materials include epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized perilla oil, epoxidized lard oil, epoxidized tallow, epoxidized tall oil, and epoxidized fish oils such as menhaden and sardine oil, as well as epoxidized sperm oil. These naturally occurring ethylenically unsaturated materials can be epoxidized by methods well known in the art to provide compositions having varying amounts of oxirane substitution.

Esters of the fatty acids and mixtures of fatty acids derived from these epoxidized naturally occurring ethylenically unsaturated fatty acid glycerides are also useful as a source of the oxirane substituted reactant. The monoand dihydric alcohol esters of such oxirane substituted fatty acids, wherein the alcohol portion of the ester is a monohydric aliphatic alcohol having 1-8 carbons, are particularly useful. Suitable monohydric alcohols providing the alcohol moiety of the epoxy fatty acid ester include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, hep-tyl and octyl alcohols. Dihydric aliphatic alcohols having 2-6 carbons are also contemplated in forming the alcohol portion of the epoxidized higher fatty acid ester. Dihydric alcohols which may be employed include ethylene glycol, 1,2-propanediol, 1,3- propanediol, dimethyl ethylene glycol, trimethylene glycol, tetramethylene glycol, up to and including hexamethylene glycol. Polyhydric alcohol (more than two hydroxy groups) esters of the oxirane containing fatty acids such as those having 3-6 carbons and three or more alcohol groups include the esters of glycerol erythritol, pentaerythritol and hexitols such as mannitol and sorbitol. Synthetic triglycerides such as epoxidized triolein, epoxidized trilinolein, and epoxidized trilinolenin are also contemplated.

The oxyalkylene oxy substituted fatty acid ester, whether prepared from the hydroxy substituted fatty acid derivative or from the oxirane substituted fatty acid derivative, is amidated with the amino alcohol by heating the reactants until the alcohol portion of the ester is replaced by the amide structure. The reaction can, if desired, be catalyzed with a small amount of potassium carbonate, potassium hydroxide, or an alkali metal lower alkoxide and the reaction can be forced to completion more rapidly by removal of the alcohol formed in the condensation reaction providing the alcohol is sufficiently volatile. Generally, amounts varying from a twofold excess of the ester to a threefold excess of the alkylolamine and, preferably between stoichiometric amounts and a twofold excess of the alkylolamine are reacted by heatirfg to a temperature of around 155 C. with the time of reaction varying inversely with the reaction temperature.

Alkylolamines useful in forming the alkylolamide include lower primary and secondary alkylolarnines which may be symmetrical, unsymmetrical, normal or iso-derivatives. N-substituted monoalkylolamides having alkyl or alkyl amino substituents are also contemplated. Thus, monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, monoisopropanolamine, diisopropanolamine, monobutanolamine, dibutanolamine, monoisobutanolamine, diisobutanolamine, monopentanolamine, dipentanolamine, methyl ethan-olamine, aminoethyl ethanolamine, and other alkylolarnines having 2-10 carbons can be employed to form the alkylolamide.

Examples I through V which follow show the preparation of the novel oxyalkylene substituted higher fatty acid alkylolamides to produce compositions having oxyalkylene and adjacent hydroxyl substituents, oxyalkylene substituted alkylolamides having solely oxyalkylene substituents and also typical but not exclusive reaction conditions utilized in forming the products.

Example I 300 grams of castor oil and 0.5 gram of sodium hydroxide were placed in a reaction vessel and the vessel was cooled while gaseous ethylene oxide was bubbled into the mixture. The temperature of the reaction vessel was maintained at 35 C. while the ethylene oxide was added. Addition of ethylene oxide was continued until the total weigh-t of the reaction mass was 550 grams. This represents the substitution of about 11 moles of ethylene oxide for each mole of castor oil. At this point the cooling was removed from the reaction vessel and the contents were heated to increase the temperature to 150 C. While this temperature was maintained, 280 grams of diisopropanolamine was added and the reaction was continued over a period of three hours at C. The product which is largely the diisopropanolamide of oxyethylated castor oil fatty acids having 11 moles of ethylene oxide substituted on the number 12 carbon of the fatty acid is a paste having substantial water solubility and exhibiting the ability to reduce the surface tension in aqueous solutions.

Example II A mixture of 320 grams of methyl dihydroxystearate was held at 42 C. Addition of ethylene oxide was continued until the reaction mixture weighed 536 grams. This represents the addition of 5 moles of ethylene oxide per mole of methyl ethyleneoxy stearate. The reaction 120 grams of monobutanolamine was added and the reaction mass was stirred and the temperature raised to 147 C. The reaction was held at this temperature for three hours. The product, which is characterized as a viscous vessel was then evacuated to inches of Hg and 83 5 liquid exhibited excellent properties as a metal working grams of aminoethyl ethanolamine containing 5 grams lubricant. of 25 sodium methylate in methanol were added. The The following example shows a comparison between reaction mixture was heated to 100 C. and the vacuum oxyalkylene substituted higher fatty acid alkylolamides was raised slowly to 28-30 inches Hg over a three-hour of the present invention as compared to the same alkylolperiod. The product was a straw colored liquid which 10 amides having no oxyalkylene substitution on the fatty was soluble in 10% aqueous salt solution and in conradical. centrated hydrochloric acid. Example VI Example 111 Samples were prepared from epoxidized methyl oleate and methoxypolyethylene glycols of molecular weight The oxyalkylene-hydroxyl substitution on adjacent 350, 550, and 750 followed by conventional aminolysis carbons in the fatty chain is illustrated in this example. with diethanolamine in the presence of sodium methylate. 2.5 grams of boron trifluoride dihydrate was dissolved They are compared to conventional oleyl diethanolamide in 350 grams of methoxy polyethylene glycol having a and stearoyl diethanolamide prepared via a comparable molecular weight of 350 (Carbowax 350). The mixture aminolysis.

TABLE I Stearoyl Oleyl Oxyethylene Substituted Oleyl Dlethanolamides Diethanolamide Diethanolamide 1 Molwt. of polyoxyethylene alcohol 350 550 750. 2 Moles ofoxyethylenm 7 11 14. 3 Physical form Solid Solid Liquid Li uid P t 4 Draves wetting time, 0.500% at 0., 3.000 gm. Over 15 min 28 seconds 25 seconds 38 seconds 42 seconds.

hook (AATCC 17-1952). 5 sugalcaemtggsion at 25 0., 0.10% (A.S.'I.M. 34.5 dynes/cm--- 33.7 dynes/cm..- 85.2 dynes/cm... 35.8 dyneslcm--- 34.9 dynes/cm. 6 R(] )ss1\1/IilesPourF0amat25C., 1.00% (A.S.T.M. Insoluble 20mm 155mm 130mm 120mm. 7 soiminii iiiwater o.s0%- 1.00% w o. Q.

was agitated while 230 grams of epoxidized soybean oil, having an oxirane oxygen content of 7% was added in increments. The agitation was continued and a homogeneous system was attained. Reaction was permitted to continue for from 15 to minutes, at which point 210 grams of diethanolamine was added and the temperature was raised to 150 C. The reaction mixture was agitated and the temperature was held at 150 C. for three hours. The product was a viscous liquid which exhibited markedly increased water solubility with equivalent or superior surface tension reducing properties as compared to similar compounds such, for example, as the diethanolamide of soybean oil fatty acids.

Example IV 5 grams of boron trifluoride etherate was added to 600 grams of polyethylene glycol 600 (polyoxyethylene glycol having a molecular weight of 600) and the mixture was agitated while 290 grams of epoxidized methyl oleate (oxirane content 515%) was added. The temperature of the reaction mixture during the substitution of the polyoxyethylene glycol on the oleic acid chain was maintained at 50 C. This temperature was held for one-half hour and at this point 100 grams of monoethanolamine and 15 grams of 25% sodium methylate in methyl alcohol was added. The temperature of the reaction mass was raised to 120 C. and the mixture was agitated. Vacuum was then applied to the system and methyl alcohol was removed as it formed. The vessel was held under a vacuum of 28-30 inches Hg for one hour and the product possessed a high degree of water solubility and a high 'amide content.

Example V 250 grams of epoxidized menhaden oil was placed in a reaction vessel with 4.5 grams of stannic chloride. The mixture was agitated and the contents cooled to C. while 60 grams of butyl carbitol was added. Cooling was continued while propylene oxide was added with the addition of propylene oxide being conducted under a pressure of 5 p.s.i. Addition of propylene oxide was continued until the reaction mass weighed 450 grams. This represents 6 moles of propylene oxide substitution for each mole of epoxidized menhaden oil. At this point Obviously, many modifications and variations of the invention as herein'before set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. Alkylolamides of higher fatty acids, the hydrocarbon chain of said fatty acids having 10-30 carbons and being substituted with alkyleneoxy radicals and hydroxyl groups on adjacent carbons in the hydrocarbon chain with the alkylol portion of said alkylolamide having 2-10 carbons.

2. The composition of claim 1 wherein the fatty acids are vegetable oil fatty acids.

3. The composition of claim 1 wherein the fatty acids are animal fatty acids.

4. The composition of claim 1 wherein the fatty acids are marine oil fatty acids.

5. Monoalkylolamides of higher fatty acids, the hydrocarbon chain of said fatty acids having 10-30 carbons being substituted with alkyleneoxy radicals and hydroxyl groups on adjacent carbons in the hydrocarbon chain with the alkyol portion of said monoalkylolamide having 2-10 carbons.

6. Dialkylolamides of higher fatty acids, the hydrocar-bon chain of said fatty acids having 1030 carbons being substituted with alkyleneoxy radicals and hydroxyl groups on adjacent carbons in the hydrocarbon chain with the alkylol portion of said dialkylolamide having 2-10 carbons.

References Cited by the Examiner UNITED STATES PATENTS 2,096,749 10/ 1937 Kritchevsky 260404 2,243,329 5/1941 De Groote et al. 2604045 X 2,883,277 4/ 1959 Beiswanger et al. 2,956,067 10/1960 De Groote et a1. 260404.5 2,965,658 12/ 1960 Kirkpatrick 260-404 3,066,159 11/1962 De Groote et a1. 260404 CHARLES B. PARKER, Primary Examiner.

I. P. BRUST, R. V. HINES, Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,281,438 October 25, 1966 Keith Liddell Johnson It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 51, for "alkylolamides" read alkylolamines column 3, line 28, for "higher fatty ester" read higher fatty acid ester column 4, line 34, for "monoalkylolamides" read monoalkylolamines column 5,

line 52, for "515%" read 5.,l5%

Signed and sealed this 5th day of September 19670 (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. ALKYLOLAMIDES OF HIGHER FATTY ACIDS, THE HYDROCARBON CHAIN OF SAID FATTY ACIDS HAVING 10-30 CARBONS AND BEING SUBSTITUTED WITH ALKYLENEOXY RADICALS AND HYDROXYL GROUPS ON ADJACENT CARBONS IN THE HYDROCARBON CHAIN WITH THE ALKYLOL PORTION OF SAID ALKYLOLAMIDE HAVING 2-10 CARBONS. 